CN1234460C - Regeneration process for solid acid catalyst - Google Patents
Regeneration process for solid acid catalyst Download PDFInfo
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- CN1234460C CN1234460C CN 03102266 CN03102266A CN1234460C CN 1234460 C CN1234460 C CN 1234460C CN 03102266 CN03102266 CN 03102266 CN 03102266 A CN03102266 A CN 03102266A CN 1234460 C CN1234460 C CN 1234460C
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Abstract
The present invention relates to a regeneration method for solid acid catalysts, which comprises the steps that eluent with halogenated alkane or halogenated aryl hydrocarbons contacts the solid acid catalysts to be regenerated, and then, the eluent is separated. Regeneration temperature is 50 to 200 DEG C, regeneration pressure is 0.1 to 4.5MPa, the liquid phase volume space velocity of the eluent is 0.1 to 20, and elution time is 1 to 48 hours. The solid acid catalysts are selected from load heteropoly acid and salt thereof, load mineral acid and salt thereof, acid oxide and zeolite molecular sieves, and cation exchange resin and solid super acid. The method of the present invention uses halogenated hydrocarbon as the eluent to regenerate the solid acid catalysts, and therefore, the present invention has the advantages of few use level of the eluent, short elution time and strong regeneration capacity for deactivated catalysts.
Description
Technical field
The present invention relates to the renovation process of solid acid catalyst.
Technical background
Bronsted acid (as hydrofluoric acid, sulfuric acid) and lewis acid (AlCl
3Deng) as catalyst extensive application in chemical industry.But because these catalyst all have severe corrosive or toxicity, equipment corrosion and problem of environmental pollution are outstanding, and operating personnel's safety is constituted potential hazard.Research with the alternative traditional liquid acid catalyst of solid acid catalyst in recent years has bigger progress, the industrialization of realization that has.Advantages such as solid acid catalyst has a little less than the equipment corrosion, and the slight and lock out operation of environmental pollution is simple.But the less stable of these solid acid catalysts, in use easy inactivation, the regeneration that how to solve decaying catalyst is the key that solid acid catalyst substitutes liquid acid catalyst.
At present the renovation process of decaying catalyst mainly contains two kinds of oxidizing process and solvent methods.Oxidizing process is a kind of common solid acid catalyst renovation process, is the incipient scorch on the catalyst to be fallen 400-550 ℃ temperature range with air.Because the ignition temperature height of oxidizing process destroys the structure of catalyst or the chemical composition of change catalyst easily.The solvent genealogy of law adopts the solvable Jiao of solvent on dissolved solid acid catalyst under certain operating condition.Solvent method is low relatively than the operating temperature of oxidizing process.At present solvent method regeneration solid acid catalyst is because regenerated solvent is poor to solvable Jiao's eluting power, causes regenerative process operating temperature height, the regenerated solvent consumption is big, the recovery time long and problem such as regeneration frequency height.
Substitute traditional liquid acid catalyst with solid acid catalyst in recent years and bigger progress is arranged as benzene and olefin alkylation reaction catalyst.The patent US 5146026 of Spain Petresa company has introduced a kind of with the method for alkane with the mixed liquor regenerated catalyst of alcohol.This method adopts sial or silicomanganese catalyst, and reaction raw materials benzene and alkane alkene feed fixed bed reactors continuously.Product makes linear alkylbenzene (LAB) through separating then.Catalyst needs periodic regeneration in this method.During regeneration with the inactivation deposit on the catalyst in the continuous wash-out fixed bed reactors of mixed liquor of alkane and alcohol.Reaction time is 12 hours, and elution time is 2-8 hour.The operation cycle of this patent is 14-20 hour, and wash-out is than being 0.3-0.8 (wash-out is than the ratio for catalyst regeneration time and reaction time under the same feedstock air speed), regeneration temperature 100-225 ℃.The patent US 5648579 of American UOP company has introduced the method for pulse benzene liquid regenerated catalyst.This method is a catalyst to fluoridize sial, and reaction raw materials (mixed liquor of benzene and alkane alkene) feeds fixed bed reactors with catalyst wash-out liquid pulse successively, with the inactivation deposit on the timely wash-out catalyst.An operation cycle of pulse charging must not reach 2 times of catalyst weight 0.1% required time greater than inactivation deposit cumulant.An operation cycle is 10-60min.The wash-out ratio is 1, regeneration temperature 150-300 ℃.Another kind of method with benzene liquid regenerated catalyst has been introduced by American UOP company in its patent US 6069285.This method adopts double-fixed bed reactor.Reaction and regeneration are carried out simultaneously.For single fixed bed reactors, reaction and regeneration hocket.Course of reaction is a raw material with the mixed liquor of benzene and alkane alkene, and regenerative process is the sedimental eluent of inactivation on the catalyst with benzene liquid.The operation cycle of this patent is 48 hours, and the wash-out ratio is 1.
In the above three kinds of catalyst recovery process, eluent is little to the sedimental amount of carrying of inactivation, causes that the eluent consumption is big, elution time is long.Eluent is poor to the power of regeneration of catalyst, and catalyst needs frequent regeneration.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, and a kind of renovation process of new solid acid catalyst is provided.This method adopts the strong halogenated hydrocarbons of eluting power to take the solid acid catalyst of regeneration of deactivated.
The renovation process of solid acid catalyst provided by the invention comprises: the eluent that will contain halogenated hydrocarbons contacts with solid acid catalyst to be regenerated, regeneration temperature is 50-200 ℃, preferred 70-150 ℃, regeneration pressure is 0.1-4.5MPa (choosing to guarantee that reaction raw materials is a liquid phase of regeneration pressure).The liquid phase volume air speed of eluent is 0.1-20, preferred 1-10.Elution time is 1-48 hour, preferred 2-24 hour.Carrying the sedimental halogenated hydrocarbons liquid of inactivation can be recycled after separating.
Said halogenated hydrocarbons is halogenated alkane or halogenated aryl hydrocarbon, preferred halogenated alkane.Halogenated alkane can be expressed as: C
nH
2n+2-mX
m, n is less than or equal to 6 natural number, and m is the integer that is less than or equal to 2n, and X is identical or different halogen fluorine, chlorine or bromine.Specifically, halogenated alkane is selected from fluoro pentane, chloro-pentane, bromo pentane, butyl fluoride, chloro-butane, butyl bromide, fluoro-propane, chloro-propane, bromo propane, fluoroethane, chloric ethane, bromic ether, fluomethane, chloromethane and bromomethane etc., preferred fluomethane and chloromethane.Halogenated aryl hydrocarbon can be expressed as: C
nH
2n-6-mX
m, n is not more than 9 and be not less than 6 natural number, and m is less than or equal to 9 natural number, and X is identical or different halogen fluorine, chlorine or bromine.Specifically, halogenated aryl hydrocarbon can be a fluorobenzene, chlorobenzene, bromobenzene, fluoro methylbenzene, chloro methylbenzene, bromomethyl benzene, fluoro ethylo benzene, chloro ethylo benzene, bromo ethyl phenenyl, fluoro propylbenzene, chloro propylbenzene and bromo propylbenzene etc.
The said eluent that contains halogenated hydrocarbons can be pure halogenated hydrocarbons, also can be that halogenated hydrocarbons content is 5-99%, the mixed liquor of preferred 10-70%, other components of mixed liquor can be aromatic hydrocarbons, alkane or alcohols, as benzene, toluene, dimethylbenzene, hexane, cyclohexane, octane, ethanol etc.
Said solid acid catalyst is selected from: carried heteropoly acid is (as phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, the silicomolybdic acid of support type, as H
3PW
12O
40, H
4PW
11O
40, H
3SiW
12O
40, H
3PMo
12O
40H
3SiMo
12O
40Deng) and its esters, carrying inorganic acid (as sulfuric acid, phosphoric acid and the alchlor etc. of support type) and its esters, acidic oxide and zeolite molecular sieve (as zeolite, diatomite, bentonite, silica and sieve and silica-sesquioxide etc.), cationic ion-exchange resin (as sulfonate resin etc.) and solid super-strong acid are (as the solid super acid catalyst of halogen-containing or sulfate radical, inferior sulfate radical, as SO
4 2-/ ZrO
2-SiO
2, SO
3H
-1/ ZrO
2-SiO
2, SbF
5/ SiO
2-WO
3, BF
5/ graphite etc.).
The inventive method is the eluent solid acid catalyst of regenerating with the halogenated hydrocarbons, and the eluent consumption is few, elution time short, and is strong to the power of regeneration of decaying catalyst.
The specific embodiment
Embodiment one:
With benzene and the synthetic linear alkylbenzene (LAB) of linear alkene, be reflected on the tubular reactor and carry out.The material of reactor is an ordinary carbon steel.The reactor lower end is a charging aperture, and the upper end is outlet.The long 400mm of reactor, external diameter 21mm, internal diameter 14mm.It is the thermocouple well of 3mm that there is a diameter in the tubular reactor axle center.Thermocouple can move axially at tubular reactor, to determine the constant temperature zone of reactor.Reaction temperature and reaction pressure all can be controlled automatically.
Adorn 10.0 gram carried heteropoly acid catalyst (HPA (40%)/SiO in the reactor
2).Catalyst grain size is the 40-60 order.The activation process of catalyst is as follows: through the normal pressure compressed air of super-dry with the flow of 200ml/hr by reactor, reactor heats up and is constant at 200 ℃ then, constant temperature is cooled to 135 ℃ after 2 hours, constant 0.5 hour.After the catalyst activation, compressed air is switched to reaction raw materials, and flow and pressure are adjusted to response value.Reaction mass is through strict dehydration.Reaction mass composed as follows: benzene/alkene mol ratio is 20, shown in the weight table 1 composed as follows of alkane alkene material.
Table 1
| Component | C 10 | C = 10 | C 11 | C= 11 | C 12 |
| Content | 6.9％ | 0.5％ | 27.5％ | 2.0％ | 34.5％ |
| Component | C = 12 | C 13 | C = 13 | Aromatic hydrocarbons | Other |
| Content | 2.2％ | 17.8％ | 1.6％ | 5.8％ | 1.2％ |
Reaction condition is as follows:
Reaction pressure: 4.5MPa
Reaction temperature: 135 ℃
Liquid phase volume air speed: 2hr
-1
The calculating of reaction conversion ratio is calculated with the bromine valency or the bromine index of material, and formula is as follows: conversion ratio=(inlet feed bromine valency X1000-outlet material bromine index)/(inlet feed bromine valency X1000) * 100%
Inlet feed bromine valency is 4.3gBr.
The concrete numerical value of bromine index and conversion ratio is as shown in table 2 below in the course of reaction.
Table 2
| Reaction time (hr) | 5 | 24 | 48 | 72 |
| Bromine index (mgBr) | 13.16 | 56.74 | 62.33 | 66.78 |
| Olefin conversion | 99.7％ | 98.7％ | 98.6％ | 98.4％ |
React after 72 hours, reaction mass is switched to the carrene liquid of dehydration, at pressure 4.5MPa, air speed 1.0hr
-1Condition under wash-out switch to reaction mass after 24 hours.Carry out 4 cycles in proper order with such reaction, regeneration.Through regeneration after catalyst reaction after 5 hours conversion ratio all greater than 99.5%.Final conversion ratio maintains more than 98%.The clean reaction time of catalyst is 288 hours.Every gram catalyst treatment material quantity is 588 milliliters.Operation cycle is 96 hours, and the wash-out ratio is 0.3.Form as shown in table 3 through taking off benzene, dealkylate afterproduct weight.
Table 3
| Linear alkyl benzene | Branched alkylbenzene | Heavy alkyl benzene |
| 88.3％ | 5.1％ | 6.6％ |
The position distribution of alkylbenzene sees Table 4:
Table 4
| 2 | 3 | 4 | 5 | 6 |
| 29.51％ | 26.09％ | 16.57％ | 20.53％ | 7.3％ |
Alkylbenzene props up chain length and sees Table 5:
Table 5
| C 10Alkylbenzene | C 11Alkylbenzene | C 12Alkylbenzene | C 13Alkylbenzene |
| 8.1％ | 32.3％ | 35.0％ | 24.7％ |
Embodiment two:
Reaction condition and raw material are formed with example one, and the reaction time is extended for 144 hours by 72 hours of a last example.Bromine index at 144 hours post-reactor outlet materials of reaction is 153.86mgBr, and conversion ratio is 96.4%.React and after 144 hours temperature of reactor is reduced to 100 ℃, reaction raw materials is switched to dehydration carrene eluent.Wash-out rose to 135 ℃ with temperature of reactor after 48 hours, and logical reaction raw materials reacts.React after 5 hours, the outlet material bromine index is 15.24mgBr, and conversion ratio is 99.6%.Reacted 144 hours, the outlet material bromine index is 170.05mgBr, and conversion ratio is 96.0%.Temperature of reactor is reduced to 100 ℃ then, at pressure 1.0MPa, air speed 2hr
-1Logical carrene eluent wash-out is 48 hours down.And then temperature of reactor risen to 135 ℃, logical reaction raw materials.React after 5 hours, the outlet material bromine index is 15.69mgBr, and conversion ratio is 99.6%.Reacted 144 hours, outlet material bromine index 193.82mgBr, conversion ratio are 95.5%.Stop reaction.Every gram catalyst treatment material quantity is 855 milliliters.Operation cycle is 192 hours, and the wash-out ratio is 0.3.
Embodiment three:
Reaction condition and raw material are formed with example one, and the reaction time shortens to 20 hours by 72 hours of example one, and carrene wash-out 4 hours then dewaters.React in proper order with this.The clean reaction time of catalyst is 300 hours.The outlet material bromine index is lower than 60.0mgBr, and conversion ratio is higher than 98.6%.Every gram catalyst treatment material quantity is 608 milliliters.Operation cycle is 24 hours, and the wash-out ratio is 0.2.
Embodiment four:
The reaction raw materials air speed is 1hr
-1, other reaction conditions are with example one.Raw material is formed also with example one.Reacted unconventional water carrene wash-out 4 hours 20 hours.React in proper order with this.The clean reaction time of catalyst is 300 hours.The outlet material bromine index is lower than 20.0mgBr, and conversion ratio is higher than 99.5%.Every gram catalyst treatment material quantity is 597 milliliters.Operation cycle is 24 hours, and the wash-out ratio is 0.2.
Embodiment five:
150 ℃ of reaction temperatures, reaction pressure 4.0Mpa, other conditions are with example one.Reacted unconventional water carrene eluent wash-out 12 hours 48 hours.The 144 hours clean reaction time of catalyst.The outlet material bromine index is not higher than 18.0mgBr, and conversion ratio is greater than 99.6%.Every gram catalyst treatment material quantity is 293 milliliters.Operation cycle is 60 hours, and the wash-out ratio is 0.25.
Embodiment six:
Reaction condition and feed composition are with example one.Reacted unconventional water chloroform eluent wash-out 4 hours 20 hours.The 140 hours clean reaction time of catalyst.The outlet material bromine index is lower than 70.5mgBr, and conversion ratio is greater than 98.4%.Every gram catalyst treatment material quantity is 286 milliliters.Operation cycle is 24 hours, and the wash-out ratio is 0.2.
Embodiment seven:
Reaction condition and feed composition are with example one.Reacted unconventional water chlorobenzene eluent wash-out 48 hours 144 hours.Behind the wash-out afterreaction 144 hours, unconventional water chlorobenzene eluent wash-out 48 hours.Stop reaction after 48 hours in reaction then.The 336 hours clean reaction time of catalyst.The outlet material bromine index is lower than 181.3mgBr, and conversion ratio is greater than 95.8%.Every gram catalyst treatment material quantity is 670 milliliters.Operation cycle is 192 hours, and the wash-out ratio is 0.3.
Embodiment eight:
Reaction condition and feed composition are with example one.Reacted unconventional water difluoromethane eluent wash-out 4 hours 20 hours.The 140 hours clean reaction time of catalyst.The outlet material bromine index is lower than 68.5mgBr, and conversion ratio is greater than 98.4%.Every gram catalyst treatment material quantity is 286 milliliters.Operation cycle is 24 hours, and the wash-out ratio is 0.2.
Embodiment nine:
Reaction condition and feed composition are with example one.Reacted unconventional water methylene bromide eluent wash-out 4 hours 20 hours.The 140 hours clean reaction time of catalyst.The outlet material bromine index is lower than 72.5mgBr, and conversion ratio is greater than 98.3%.Every gram catalyst treatment material quantity is 286 milliliters.Operation cycle is 24 hours, and the wash-out ratio is 0.2.
Embodiment ten:
Reaction condition and feed composition are with example one.Reacted the unconventional aqueous solution (carrene and benzene, carrene/benzene mole ratio is 1: 1) eluent wash-out 4 hours 20 hours.The 140 hours clean reaction time of catalyst.The outlet material bromine index is lower than 74.5mgBr, and conversion ratio is greater than 98.3%.Every gram catalyst treatment material quantity is 286 milliliters.Operation cycle is 24 hours, and the wash-out ratio is 0.2.
Embodiment 11:
Reaction condition and feed composition are with example one.Reacted unconventional water fluorine chlorine two generations methane eluent wash-out 4 hours 20 hours.The 140 hours clean reaction time of catalyst.The outlet material bromine index is lower than 71.5mgBr, and conversion ratio is greater than 98.3%.Every gram catalyst treatment material quantity is 286 milliliters.Operation cycle is 24 hours, and the wash-out ratio is 0.2.
Embodiment 12: acetate/propylene esterification synthesis of acetic acid isopropyl ester
Horminess glass tube with internal diameter 8mm is fixed bed reactors, S0
4 2-/ ZrO
2-SiO
2The catalyst loading amount is 5 grams.Propylene gas is a polymer grade, and acetate is pure for analyzing, and propylene/acetate mol ratio is 2: 1, and the ethene air speed is 1.0Hr
-1, 140 ℃ of reaction temperatures, pressure 1.0MPa.React after 0.5 hour, the acetate conversion ratio is 48.6%, and the selectivity of isopropyl acetate is 98.5%.React after 100 hours, the acetate conversion ratio reduces to 35.3%, and the selectivity of isopropyl acetate is 98.0%.Stop reaction then, be cooled to 100 ℃, with 1,2-dichloroethanes solvent (analyzing pure) under the pressure of 0.1MPa with the flow wash-out SO of 30M1/Hr
4 2-/ Zr
2-Si
2Behind the catalyst 3 hours, purged 2 hours down at 100 ℃ with nitrogen.Continue acetate/propylene esterification then, react after 0.5 hour, the acetate conversion ratio is 48.5%, and the selectivity of isopropyl acetate is 98.4%.
Embodiment 13: oligomerization of propene
With HPA (40%) SiO
2Be catalyst.Reactor inside diameter 14mm, apparatus with catalyst inside 80 grams.200 ℃ of reaction temperatures, reaction pressure 4.0MPa, the propylene mol ratio is 1: 1, mass space velocity 2.0Hr
-1React after 1.0 hours, propylene conversion is 83.5%.React after 48 hours, propylene conversion reduces to 74%, and nonene and laurylene account for 80% of product.Reaction temperature is reduced to 60 ℃ then, reaction pressure 1.0MPa, under the condition of air speed 2.0 with 1,1,1-trichloroethanes wash-out catalyst 4 hours.Carry out propylene oligomerization then.Catalyst after regeneration is 82.9% to propylene conversion, and nonene and laurylene account for 80% of product.
Embodiment 14: etherification reaction
With AlCl
3(20%)/SiO
2Be catalyst, catalyst loading amount 10.0 grams.75 ℃ of reaction temperatures, reaction pressure 5.0Mpa.Methanol quality and oxirane mark are 99.9%, and the mol ratio of methyl alcohol/oxirane is 2: 1, air speed 2.0.The conversion ratio of reaction initial activity oxirane is 100%.React after 48 hours, the oxirane conversion ratio is 93.0%.Keep the origin operation condition to continue reaction after 2 hours with carrene (analyzing pure) wash-out catalyst, the conversion ratio of oxirane is 99.6%.Initial reaction stage, reaction see the following form after 48 hours and through regeneration afterproduct composition.
Etherification reaction product (quality) is formed (%) and is seen Table 6:
Table 6
| Oxirane | Methyl alcohol | Glycol monoethyl ether | Diethylene glycol monomethyl ether | Triethylene glycol monomethyl ether | The TEG monomethyl ether | Accessory substance (bis ether etc.) | |
| Initial reaction stage | 0.0 | 46.67 | 40.51 | 9.48 | 1.32 | 0.16 | 1.86 |
| After 48 hours | 3.38 | 47.69 | 38.28 | 8.85 | 1.07 | 0.14 | 3.00 |
| After the regeneration | 0.14 | 46.64 | 40.47 | 9.44 | 1.30 | 0.15 | 1.87 |
Claims (6)
1. the renovation process of a solid acid catalyst, comprise: the eluent that will contain halogenated aryl hydrocarbon contacts with solid acid catalyst to be regenerated, separation eluent then, regeneration temperature is 50-200 ℃, regeneration pressure is 0.1-4.5MPa, the liquid phase volume air speed of eluent is 0.1-20, and elution time is 1-48 hour, and said halogenated aryl hydrocarbon is expressed as C
nH
2n-6-mX
m, n is not more than 9 and be not less than 6 natural number, and m is less than or equal to 9 natural number, and X is identical or different halogen fluorine, chlorine or bromine.
2. according to the described renovation process of claim 1, it is characterized in that said regeneration temperature is 70-150 ℃, the liquid phase volume air speed of eluent is 1-10, and elution time is 2-24 hour.
3. according to the described renovation process of claim 1, it is characterized in that said halogenated aryl hydrocarbon is selected from fluorobenzene, chlorobenzene, bromobenzene, the fluoro methylbenzene, chloro methylbenzene, bromomethyl benzene, fluoro ethylo benzene, chloro ethylo benzene, bromo ethyl phenenyl, fluoro propylbenzene, chloro propylbenzene and bromo propylbenzene.
4. according to the described renovation process of claim 1, it is characterized in that the said eluent that contains halogenated aryl hydrocarbon is pure halogenated aryl hydrocarbon, or the mixed liquor of halogenated aryl hydrocarbon and aromatic hydrocarbons, alkane or alcohols composition, the content of halogenated aryl hydrocarbon is 5-99% in the mixed liquor.
5. according to the described renovation process of claim 4, it is characterized in that, the mixed liquor that the said eluent that contains halogenated aryl hydrocarbon is made up of halogenated aryl hydrocarbon and benzene,toluene,xylene, hexane, cyclohexane, octane or ethanol, the content of halogenated aryl hydrocarbon is 10-70% in the mixed liquor.
6. according to the described renovation process of claim 1, it is characterized in that said solid acid catalyst is selected from carried heteropoly acid and its esters, carrying inorganic acid and its esters, acidic oxide and zeolite molecular sieve, cationic ion-exchange resin and solid super-strong acid.
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|---|---|---|---|
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102553659B (en) * | 2010-12-30 | 2014-05-28 | 中国石油化工股份有限公司 | Regeneration method of solid super acidic catalyst |
| CN104588103B (en) * | 2013-11-03 | 2016-10-26 | 中国石油化工股份有限公司 | A kind of catalyst for synthesizing 2-alkyl-anthraquinone and its preparation method and application |
| CN104001554A (en) * | 2014-06-14 | 2014-08-27 | 福州大学 | Method for regenerating catalysts for olefin esterification reaction and hydration reaction |
| JP6505866B2 (en) * | 2015-12-03 | 2019-04-24 | 旭化成株式会社 | Process for producing propylene or aromatic hydrocarbon |
| CN106866398A (en) * | 2017-02-27 | 2017-06-20 | 天津大学 | A kind of method of 2 EAQs of industrial continuous production |
| CN108714436B (en) * | 2018-08-03 | 2021-03-30 | 江苏扬农化工集团有限公司 | Method for recovering activity of heteropoly acid catalyst for synthesizing epoxy chloropropane |
| CN111203287A (en) | 2018-11-21 | 2020-05-29 | 内蒙古伊泰煤基新材料研究院有限公司 | Regeneration method of benzene alkylation solid acid catalyst |
| CN110935434A (en) * | 2019-12-09 | 2020-03-31 | 北京石油化工学院 | Catalyst for preparing nonene and dodecene by propylene oligomerization and preparation method and application thereof |
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